Method of preparing valuable nitrogenous condensation products



Patented Feb. 23, 1943 METHOD OF PBEPARDTG- VALUABLE NI- TROGENOUS CONDENSATION PRODUCTS Heinrich Ulrich and Karlhugo Kuespert, Ludwigshaien-on-the-Bhine, Germany, assignors, by memo assignments, to General Aniline 8r Film Corporation, New York, N. Y., a corporation of Delaware No Drawing. Application May 12, 1938, Serial No.

207,504. In Germany May 18, 1937 3Claims. (01.

This invention relates to a new method of preparing valuable nitrogenous condensation products.

We have found that valuable nitrogenous con;- densation products can be prepared by causin compounds of the formula X-R (in whlch'R is an alkyl, cycloaikyl, aralkyl or aryl radicle or a Suitable compounds containing sulphuric acid,

ester groups are for example octodecyl or octoheterocyciic radicle, which may be substituted,

and X is an exchangeable substituent, i. c. it may be a halogen atom or an exchangeable group, as 101' example a --O-CO-Cl group or a --SO:H group (free or as salt) to act with the aid of metal compounds having an alkaline action on organic compounds containing in the molecule only such nitrogen atoms as are free from hydrogen directly attached thereto and containing at least one aikylol group attached to basic nitrogen.

Among suitable metal compounds having an alkaline action may be mentioned the oxides, hydroxides or alcoholates of alkali or alkaline earth metals, and also weakly alkaline salts, such as sodium or potassium carbonate, sodium acetate and also sodamide.

Suitable alkylol' compounds of the kind deflned are for example triethanolamine, the tripropanolamines, ethyldiethanolamine, cyclohexyl-diethanolamine, dlethanolaniline, N-ethanolpiperidine, benzyl-dlethanolamine, N-ethanoimorpholine, N ethanoltetrahydroquinoline, diethanoldiethybethylene diamine, tetra-ethanol ethylene diamine, tetra ethanol paradecenyl alcohol sulphuric acid ester, butyl polyglycol ether sulphuric acid ester, ethylene chlorhydrin sulphuric acid ester, which are best used in the form of their salts, advantageously v the sodium salts.

The alkylol compounds may first be reacted with the alkaline-acting metalccmpounds, as for example the oxides, hydroxides or alcoholates of alkali or alkaline earth metals inthe presence or absence of diluents or solvents. When working in the presence of water, it is preferable to remove the same completely or to a great ex;-

tent towards the end, advantageously by distilling it off. When working in the presence of.

indifferent solvents, as for examplebenzene or toluene, these may be subsequently distilled off or the following reaction with compounds of the formulaX-R. may be carried out inthe presence of the same. The amount of alkaline-reacting metal compounds to be. used depends on what amount of the halogen compounds or the line-reacting metal compounds often takes place phenylene diamine and the like. Compounds of the said kind which contain further substituents, as for example carboxylgroups (in the free form or combined in the form of salts, amides or esters) or ether residues or polyether chains, may also be used.

'- .Among suitable compounds of the formula -IK---li'.,there may be mentioned methyl iodide,

ethyl bromide, ethylene chlorhydrin, epichlorhydrin, beta, beta-'-dichlordiethyl ether, butyl chloride, dodecyl bromide, octodecyl bromide,-

alkyl chloride mixtures desired from the hydrocarbons having the carbon skeleton of the fatty acid mixtures contained in naturally occuring fats, chlorinated. petroleum fractions, cyclohexyl even at room temperature, so that sometimes cooling may be preferable or even necessary. When employing compounds which react with difficulty it is often advantageous to work while heating in order to carry out the reaction completely. The water split off or, when using alcoholates, the alcohol split off during the reaction is preferably distilled oil, if desired with the co-employment of inert gases or in vacuo.

.The reaction may be carried out in they presence chloride, benzyl chloride, nitrochlorbenzene and chiorpiperidine. Compounds having exchangeable groups may also be used, as for example chlorocarbonic acid esters, as for example octodecyl chlorocarbonlc acid ester from which carbon dioxide is frequently split off during the reaction so that ether-like combination of the -ample by means of ethylene oxide or epichlor of diluents or solvents. When using components or diluents of low boiling point it may be advantageous or necessary to work under pressure.

Instead of first reacting the compounds containing alkylol groups separately with the alkali hydroxides or the other alkaline-reacting metal compounds and then with compounds of the formula RF-X, the alkylol compounds may be brought into reaction with the compounds of the formula X-R in the presence of the alkali hydroxides or the like. The solubility of the roducts may be increased, when desired, by sulphonation or hydroxyalkylation, as for exhydrin.

Especially valuable products are obtained when acyl groups are introduced before or after alkyl radicle contained in the ester takes place. 66 the said condensation. When starting-from alv position:

the alnlol groups intended for the etheriilcation iurther hydroxyl groups (which may also be contained in alkylol groups), the acyl groups may enter wholly or in part into these hydroxyl groups. The acylation may also be eile'cted on nitrogen.

The radicles or ronmc acid. acetic acid,.butyr ic acid, oleic-"acidybenzoic acid, phthalic acid, ma lonic acid, of quinoline carboxylic' acids, taurine,

toluene sulphonic acids or naphthalene sulphonic 8,812,186 kylol compounds which contain, in addition. to:

. The reaction product of 150 parts 0! triethanv olamine'and 80 parts of caustic soda describedin Example 1' is treated under the conditions described in Example 1 with 665 parts or octodeoyl chlorocarbonic acid ester.' The. product soluble- 4 in acid thus formed contains in the molecule two acids may be introduced, the free acids or suitable derivatives, as for example the acid halides, esters or anhydrides, being used and working radicles derived from octodecyl alcohol of which one is probably combin'ed'in the form of an 06W decyl carbonic acid ester radicle and the other in the form of an octodecylether radicle, each to an ethanol group of the triethanolamine.

By using 40 parts of caustic soda instead 01 80 parts and by using 333 parts of ootodecyl chlorocarbonic acid. ester instead of 665 parts. a compound is obtained which contains only one radicle derived from the octodecyl chlorocarbonic acid ester.

' Instead of octodecillchlorocarbonic ester there may also be used octyl chlorocarbonic acid ester or dodecyl chlorocarbonic acid ester.

Example 3 150 parts of triethanolamine. 290 parts of octodecyl chloride and 42 parts of caustic soda'are mixed while stirring and the mixture-is heated may be used with special advantage in the prep aration or improvement of artificial fibres. Many of them, in particular the products or low molecular weight, may serve as mercerizing wetting agents. The products are also suitable tor increasing the capacity of artificial fibres for being dyed and as softening agents for the same. The following examples will further illustrate how the said invention may be carried out in practice, but the invention is not restricted to these examples. The parts are by weight.

Example 1 80 parts a: caustic soda are added to 150 parts of] triethanolamine. Heating thus takes place and a solid white product is formed. 580 parts to from 130 to 140 C. so that'the water formed distils oil. The octodecyl ether of. triethanolamine is obtained- 1 Example! 150 parts of vtriethanolaxnine are stirred with 78 parts of sodamide while heating gently until v the evolution of ammonia ceases.

The whole is then heated with 580 parts or octodecyl chloride to from 130 to 140 C. and kept at this tempera.-

'- ture until chlorine can no longer be detected in oi'octodecyl chloride are then added and the,

whole heated in vacuo to about 120 C. The water formed in the reactionis thus distilled ofl.

product is mixed 'while still warm with about'IOOO parts of water,-the base or the comthus formed being thus separated in a practically pure form. It may be converted by the addition of acids, as for example formic acid or hydrochlorlc acid, into salts of better solubility which arevaluable textile assistants. They may also be used in textile improvements in emulsified form.

By using40 parts 01 caustic soda and 290 parts of octodecyl chloride instead oi the abovementioned. amounts, the compound:

is obtained.

Instead of heating in vacuo, a current of nitrogen may be led through. The reaction is advantageously carried out while stirring.

Instead of octodecyl chloride there may also be'used monoor tri-chlor-hard-paraflln-wax or the alkyl chloride mixture of the hydrocarbons having the carbon skeleton of the fatty acids of palm kernel or train oil, or octodecenyl alcohol sulphuric acid ester.

the base formed. The product forced is the dioctodec'yl other of triethanolamine.

Example 5 150 parts of triethanolamine are mixed with 250 parts of ethylene chlorhydrin glycol ether.-

165 parts of anhydrous sodium acetate or 200 parts of potassium carbonate are then added and the whole heated to [about ,140 C. the water of reaction thus being distilled oil. The product is suitable as a wetting agent after sulphonation.

z mn e 6. f

e parts of dioctd'decyl triethanolamine ether are heated with 284 parts of stearic acid in vacuo at 140 C. until water no longer distils oil.

The product thus'obtainable, which'is soluble in organic solvents, is suitable for rendering textiles water-repelling.

Example 7 398partS or stearic acid diethanoiamide (obtainedby heating stearic acid and diethanolamine to 150 C.) are mixed with 275 parts of a technical mixture oi cetyl and'octodecyl chlorides. 42 parts of caustic soda are added and the whole heated to about 140 C. for 20 hours.

The waxy product formed is suitable as a hydro phobing agent; by introducing water-solubilizing groups, excellent textile assistants having opening and softening properties are obtained.

Example 8 150 parts of technical triethanolamine (or 236 parts of tetra-ethanol ethylene diamine) are mixed with 270 parts of technical octodecyl chloride and heated to C. with 42 parts of caustic soda while stirring. I After separating the common salt formed, the reaction product has added to it 285 parts of stearic acid and is heated in vacuo at from 150 to 160 C. An excellent emulsifying and softening agent is obtained.

Instead of stearic acid there may also be used for example anhydrides of paraffin oxidation fatty acids which contain from about 6 to 10 carbon atoms in the molecule.

What we claim is:

1. The process ,for producing nitrogenous others which comprises causing an alkyl halide to act upon a polyalkylol amine selected from the class consisting of tri-ethanolamine, ethyl-diethanolamine, cyclohexyl-diethan0lamine, diethanol aniline and benzyl-diethanolamine with the aid of a metal compound having an alkaline action and selected from the class consisting of alkali metal and alkaline earth metal compounds.

2. The process as defined in claim 1 wherein the polyalkylol amine is tri-ethanolmine.

3. The process as defined in claim 1 wherein 10 the alkyl halide is octodecyl chloride.

HEINRICH ULRICH. KARLHUGO KUESPERT.

Certificate of Correction Patent No. 2,312,135. Feb uary 23, 1943.

HEINRICH ULRICH ET AL.

It is hereby. certified that errors appear in the printed specification of the above numbered patent requiring correction as follows: Page 1, first column, line 44, for desired read derivedfpage 2, second column, line 38, Example 4, for forced read formed; and that the said Letters Patent should be read with these corrections therein that the same may conform to the record of the case in the Patent Oflice Signed and sealed this 15th day of April; A. D. 1947.

LESLIE FRAZER,

First Assistant Gowmnz'ssioner of Peter; t5. 

